Radiation-modified poly (tetrafluoroethylene) resin feeds and a process for producing the same

ABSTRACT

Unsintered poly(tetrafluoroethylene) resin feeds are treated with ionizing radiation in an absorbed dose of no more than 1,000 Gy at room temperature in air so that only the melting temperature of the resin feeds is shifted toward the lower end without changing the quantities of heat of fusion and crystallization.

BACKGROUND OF THE INVENTION

[0001] This invention relates to an improvement of thermal properties ofpoly(tetrafluoroethylene) resin feeds by ionizing radiations. Moreparticularly, the invention relates to a process for producingradiation-modified poly(tetrafluoroethylene) resin feeds by applyingionizing radiations to unsintered poly(tetrafluoroethylene) resins undermild conditions so that only their melting temperature is shifted to thelower end without changing the quantities of heat of fusion andcrystallization. The thus modified poly(tetrafluoroethylene) resin feedsare characterized in that their moldings have the same meltingtemperature, heat of fusion, crystallization temperature and heat ofcrystallization as the moldings of the unirradiatedpoly(tetrafluoroethylene) resin feeds. The invention also relates to theradiation-modified poly(tetrafluoroethylene) resin feeds produced by theprocess.

[0002] Poly(tetrafluoroethylene) resins are engineering plastics havinghigh resistance to heat, chemicals and friction, high water repellency,good lubricating property and high electrical insulation. Because ofthese features, poly(tetrafluoroethylene) resins have heretofore beenused in various industrial and consumer applications including electricwire coatings, tubes, pipes, packings, gaskets, linings, insulationtape, bearings and roofing membranes for air domes.

[0003] However, unlike the other polymeric materials,poly(tetrafluoroethylene) resins are seldom molded into various shapeson their own. For the very reason that they have high heat and chemicalresistance, poly(tetrafluoroethylene) resins are difficult to shape byheating or dissolving in solvents.

[0004] With a view to improving the moldability ofpoly(tetrafluoroethylene) resins, it has been attempted to modify themby partial replacement of the tetrafluoroethylene molecules with acopolymerizable component. However, the introduced copolymerizablecomponent not only causes substantial changes in thermal properties,such as the quantities of heat of fusion and crystallization, of thepoly(tetrafluoroethylene) resins but also impairs their purity, thuscausing deterioration in various characteristics of their moldings.

[0005] Of the various polymeric materials known today,poly(tetrafluoroethylene) resins are the easiest to deteriorate uponradiation exposure and the mechanical characteristics of their moldingsdecrease with absorbed dose whereas the quantities of heat of fusion andcrystallization increase as more molecular chains are severed. Needlessto say, poly(tetrafluoroethylene) resins in bulk powder form havesubstantially the same sensitivity to radiation as when they are shapedinto moldings; following the exposure to radiation, the quantities ofheat of fusion and crystallization increase as more molecular chains aresevered and the mechanical characteristics of shapes molded from theirradiated poly(tetrafluoroethylene) resins are also inferior to thoseof the unirradiated resins. These effects of radiations are currentlyused to prepare a wax of poly(tetrafluoroethylene) resins by decomposingthem.

[0006] It has recently been shown that poly(tetrafluoroethylene) resinsare crosslinked by applying ionizing radiation in a special environment,i.e. at elevated temperature in the absence of oxygen. The crosslinkedresins have higher heat resistance but, on the other hand, theirmoldability is impaired.

SUMMARY OF THE INVENTION

[0007] It is, therefore, the principal object of the invention toimprove the moldability of poly(tetrafluoroethylene) resins by thesimple means of applying radiation such that their purity is retainedand that only their melting temperature is shifted toward the lower endwithout changing the quantities of heat of fusion and crystallizationfrom those of unsintered poly(tetrafluoroethylene) resins.

[0008] More specifically, the invention provides radiation-modifiedpoly(tetrafluoroethylene) resins which are characterized in that theirmoldings have the same melting temperature, heat of fusion,crystallization temperature and heat of crystallization as the moldingsof the unirradiated poly(tetrafluoroethylene) resin feeds. The inventionalso provides a process for producing such radiation-modifiedpoly(tetrafluoroethylene) resin.

[0009] In order to attain the stated object, the present inventorsapplied ionizing radiations to unsintered poly(tetrafluoroethylene)resins in bulk powder form under various conditions and made a closestudy of the relationship between the exposure conditions and each ofthe thermal properties, such as melting temperature, heat of fusion,crystallization temperature and heat of crystallization, of the resinsboth before and after shaping. As a result of their intensive studies,the inventors found the following new fact: when unsinteredpoly(tetrafluoroethylene) resin feeds were exposed to ionizing radiationin an absorbed dose of no more than 1,000 Gy at room temperature in air,only their melting temperature was shifted toward the lower end withoutchanging the quantities of their heat of fusion and crystallization,whereby their moldability was improved; in addition, the moldings of theirradiated resin feeds had identical values of thermal properties, suchas melting temperature, heat of fusion, crystallization temperature andheat of crystallization, to those of the moldings prepared from theunirradiated resin feeds. The present invention has been accomplished onthe basis of this finding.

[0010] The present inventors previously invented a method in whichpoly(tetrafluoroethylene) resins were exposed to ionizing radiation,thereby producing radiation-modified poly(tetrafluoroethylene) resinshaving increased tear strength and an application for obtaining patenton this invention was already filed (Japanese Patent Application No.2000-155902). The present invention provides a very effective method ofusing radiations in that the moldability of poly(tetrafluoroethylene)resin feeds could be improved by only shifting the melting temperatureof unsintered resin feeds toward the lower end without affecting thethermal properties of the moldings to be prepared.

BRIEF DESCRIPTION OF THE DRAWINGS

[0011]FIG. 1 is a graph showing the result of DSC (differential scanningcalorimetry) conducted to measure thermal properties of 500-Gyirradiated poly(tetrafluoroethylene) in bulk power form in a temperaturerange of 270-390° C. with the temperature rising at a rate of 10°C./min; and

[0012]FIG. 2 is a graph showing the result of DSC conducted to measurethermal properties of a comparative sample [unirradiatedpoly(tetrafluoroethylene) resin feed in bulk powder form] in atemperature range of 270-390° C. with the temperature rising at a rateof 10° C./min.

DETAILED DESCRIPTION OF THE INVENTION

[0013] In the invention, a poly(tetrafluoroethylene) resin feed istreated by an ionizing radiation. To be more specific, a dried powder ofpoly(tetrafluoroethylene) resin or a liquid called “dispersion” in whicha powder of poly(tetrafluoroethylene) resin is dispersed uniformly istreated by an ionizing radiation to give an absorbed dose of 1-1,000 Gyin a temperature range of −30˜50° C. near ordinary or room temperature,preferably not higher than 19° C., and in air.

[0014] The term “poly(tetrafluoroethylene) resin feed” as used hereinmeans dried powders of poly(tetrafluoroethylene) resins obtained byemulsion polymerization or suspension polymerization, said powders beingoptionally granulated or dispersed uniformly in solvents or wetted withsolvents. The powders or dispersions of poly(tetrafluoroethylene) resinsneed not be entirely treated with ionizing radiation and the intendedadvantages and object of the invention can be attained even if saidpowders or dispersions are mixed in suitable proportions with thepowders or dispersions of unirradiated poly(tetrafluoroethylene) resins.

[0015] The dispersion medium, or the liquid in which the powders ofpoly(tetrafluoroethylene) resin feeds can be dispersed efficiently, maybe exemplified by mixed solvents such as those consisting ofwater/emulsifier, water/alcohol, water/acetone, andwater/alcohol/acetone; suitable dispersion media can be easily selectedor prepared by skilled engineers in the art who are familiar withdispersion media.

[0016] The emulsifier may be exemplified by an aqueous colloidalsuspension of PTFE which has a nonionic surfactant such as NISSAN NONIONHS208 (trademark) or an anionic surfactant added in a few percent to theresin, or a dispersion having an aqueous solution of phosphoric acid orchromic acid added to the aqueous colloidal suspension of PTFE in orderto provide ease in a subsequent step of bonding the resin film to ametal substrate by stoving.

[0017] The ionizing radiation to be used in the invention may beexemplified by electron beams, x-rays, γ-rays, neutron beams andhigh-energy ions which may be used either alone or in admixture. Thedose rate, or the amount of radiation applied per unit time, may be ofany suitable values that can be easily chosen by skilled engineers inthe art.

[0018] The purpose of the invention can be easily attained by treatingthe poly(tetrafluoroethylene) resin feed with ionizing radiation in air.If desired, a certain kind of reactive gas or inert gas mayintentionally be added to air to create a special atmosphere so that aspecified function or property is conferred to the radiation-modifiedpoly(tetrafluoroethylene) resin or that a property such as waterrepellency the poly(tetrafluoroethylene) initially possess isattenuated; this practice is also included in the scopey of theinvention. Therefore, the term “air” as defined herein covers not onlythe ordinary air in the atmosphere but also atmospheres createdintentionally as described above by adjusting or modifying thecomposition of the ordinary atmospheric air.

[0019] The following examples are provided for the purpose of furtherillustrating the present invention but are in no way to be taken aslimiting.

EXAMPLE 1

[0020] A commercial fine powder of poly(tetrafluoroethylene) resinprepared by emulsion polymerization (CD 090 of Asahi GlassFluoropolymers Co., Ltd.) was used as a resin feed and put into paperenvelopes. The respective samples were irradiated with γ-rays for 0.5,2.5 and 5 hours at a dose rate of 200 Gy/h in air at room temperature,thus producing feed powders treated with γ-rays to absorbed doses of100, 500 and 1,000 Gy.

[0021] Differential scanning calorimetry (DSC) provides a simple toolfor examining thermal properties of the poly(tetrafluoroethylene) resinboth before sintering (in an unirradiated state) and after molding (inan irradiated state). The first run of scan with temperature elevationsimulates thermal properties after polymerization reaction whereas thesecond run of scan with temperature elevation simulates thermalproperties after molding.

[0022] Thermal properties of the feed powder irradiated with 500 Gy ofγ-rays were measured by DSC in a temperature range of 270-390° C. withthe temperature rising at a rate of 10° C./min and the result is shownin FIG. 1. For comparison, the same measurement was made on anunirradiated poly(tetrafluoroethylene) resin powder and the result isshown in FIG. 2. The feed powders treated with γ-rays to absorbed dosesof 100, 500 and 1,000 Gy were subjected to the first and second runs ofDSC and the melting temperature and the quantity of heat of fusion weremeasured for each sample; the results are shown in Table 1.

[0023] In the first run of DSC, the irradiated feed powders exhibitedlower melting temperatures than the unirradiated sample but there waslittle change in the quantity of heat of fusion. In the second run ofDSC, there were no changes in thermal properties and all samplesincluding the comparative sample had the same data.

[0024] The term “heat flow rate” on the vertical axes of FIGS. 1 and 2represents a heat balance in thermal analysis by DSC, or the heat inputto or output from the resin sample as it is heated or cooled with thetemperature rising or falling at a constant rate. The term “resin beforesintering” refers to the case of using an unsintered shape as green PTFEand the term “resin after sintering” refers to the case of using a shapeas a plastic after it is sintered, i.e. heat treated at the meltingpoint or above. TABLE 1 Results of Analysis by DSC of Feed Powders forDifferent Doses of Gamma-Rays First run Second run Melting Heat ofMelting Heat of temperature fusion temperature fusion Unirradiated 338.168.5 325.1 30.1  100 Gy 337.7 68.1 325.3 30.8  500 Gy 337.0 66.7 325.130.2 1000 Gy 336.4 67.5 325.8 30.1

EXAMPLE 2

[0025] A commercial molding powder of poly(tetrafluoroethylene) resinprepared by suspension polymerization (G 163 of Asahi GlassFluoropolymers Co., Ltd.) was used as a resin feed and put into paperenvelopes. The respective samples were irradiated with γ-rays for 1, 3and 5 hours at a dose rate of 100 Gy/h in air at room temperature, thusproducing feed powders treated with γ-rays to absorbed doses of 100, 300and 500 Gy.

[0026] The feed powders treated with γ-rays to absorbed doses of 100,300 and 500 Gy were subjected to the first and second runs of DSC in atemperature range of 270-390° C. with the temperature rising at a rateof 10° C./min and the melting temperature and the quantity of heat offusion were measured for each sample; the results are shown in Table 2.

[0027] In the first run of DSC, the irradiated feed powders exhibitedlower melting temperatures than the unirradiated sample but there waslittle change in the quantity of heat of fusion. In the second run ofDSC, there were no changes in thermal properties and all samplesincluding the comparative sample had the same data. TABLE 2 Results ofAnalysis by DSC of Feed Powders for Different Doses of Gamma-Rays Firstrun Second run Melting Heat of Melting Heat of temperature fusiontemperature fusion Unirradiated 342.6 63.7 325.6 21.3 100 Gy 338.4 62.4325.9 21.7 300 Gy 337.0 63.2 326.1 22.2 500 Gy 335.9 62.0 325.8 22.1

EXAMPLE 3

[0028] A commercial molding powder of poly(tetrafluoroethylene) resinprepared by suspension polymerization (G 350 of Asahi GlassFluoropolymers Co., Ltd.) was used as a resin feed and put into paperenvelopes. The respective samples were irradiated with γ-rays for 12, 30and 60 minutes at a dose rate of 1,000 Gy/h in air at room temperature,thus producing feed powders treated with γ-rays to absorbed doses of200, 500 and 1,000 Gy.

[0029] The feed powders treated with γ-rays to absorbed doses of 200,500 and 1,000 Gy were subjected to the first and second runs of DSC in atemperature range of 270-390° C. with the temperature rising at a rateof 10° C./min and the melting temperature and the quantity of heat offusion were measured for each sample; the results are shown in Table 3.

[0030] In the first run of DSC, the irradiated feed powders exhibitedlower melting temperatures than the unirradiated sample but there waslittle change in the quantity of heat of fusion. In the second run ofDSC, there were no changes in thermal properties and all samplesincluding the comparative sample had the same data. TABLE 3 Results ofAnalysis by DSC of Feed Powders for Different Doses of Gamma-Rays Firstrun Second run Melting Heat of Melting Heat of temperature fusiontemperature fusion Unirradiated 342.7 63.4 325.8 22.1  200 Gy 339.6 60.8325.8 21.9  500 Gy 338.0 62.7 325.8 22.4 1000 Gy 337.3 62.3 325.4 23.1

EXAMPLE 4

[0031] The powder irradiated with 1000 Gy of γ-rays in Example 3 wasmixed uniformly at a ratio of 1:1 with an unirradiated powder of G 350at a temperature of 15° C. to prepare a feed powder. Thermal propertiesof the feed powder were measured by DSC in a temperature range of270-390° C. with the temperature rising at a rate of 10° C./min were.The feed powder was subjected to the first and second runs of DSC andthe melting temperature and the quantity of heat of fusion weremeasured; the results are shown in Table 4. TABLE 4 Results of Analysisby DSC of Feed Powders First run Second run Melting Heat of Melting Heatof temperature fusion temperature fusion Unirradiated 342.7 63.4 325.822.2 1:1 Mixture 338.2 63.8 325.6 22.5

[0032] If poly(tetrafluoroethylene) resin feeds after polymerizationreaction but before sintering are treated with ionizing radiation by themethod of the invention, only their melting temperature is shiftedtoward the lower end without changing the quantities of their heat offusion and crystallization. As a result, the moldability of the feeds isso much improved that the moldings prepared from them are the same asthose from the unirradiated resin feeds not only in the meltingtemperature and the quantity of heat of fusion but also in thecrystallization temperature and the quantity of heat of crystallization.In addition, the improved moldability of the poly(tetrafluoroethylene)resins is anticipated to bring out new properties. What is more, theinvention does not rely upon chemical means of modification such ascopolymerization and the inherent good properties of thepoly(tetrafluoroethylene) resins remain intact; this will help furtherexpand the scope of their utility.

What is claimed is:
 1. A radiation-modified poly(tetrafluoroethylene) resin feed the melting temperature of which has been shifted toward the lower end without changing the quantities of heat of fusion and crystallization.
 2. The radiation-modified poly(tetrafluoroethylene) resin feed according to claim 1, wherein a molding prepared from said resin feed is the same as a molding from an unirradiated resin feed not only in the melting temperature and the quantity of heat of fusion but also in the crystallization temperature and the quantity of heat of crystallization.
 3. A molding resin feed composition comprising the radiation-modified poly(tetrafluoroethylene) resin feed according to claim 1 and an unirradiated powder of poly(tetrafluoroethylene) resin or a radiation-crosslinked poly(tetrafluoroethylene) resin.
 4. A process for producing a radiation-modified poly(tetrafluoroethylene) resin feed by treating an unsintered poly(tetrafluoroethylene) resin feed with an ionizing radiation in an absorbed dose of no more than 1,000 Gy at room temperature in air so that only the melting temperature of the resin feed is shifted toward the lower end without changing the quantities of heat of fusion and crystallization.
 5. The process according to claim 4, wherein the ionizing radiation is applied at a temperature near ordinary or room temperature.
 6. The process according to claim 4 or 5, wherein the ionizing radiation is selected from electron beams, x-rays, γ-rays, neutron beams and high-energy ions which are used either independently or in admixture.
 7. The process according to any one of claims 4-6, wherein the poly(tetrafluoroethylene) resin feed is in powder form.
 8. The process according to any one of claims 4-7, wherein the poly(tetrafluoroethylene) resin feed is a dried powder of poly(tetrafluoroethylene) resin obtained by emulsion polymerization or suspension polymerization, which is optionally granulated or dispersed uniformly in solvents or wetted with solvents. 